Method of forming mirrors by surface transformation of empty spaces in solid state materials

ABSTRACT

A multi-layered reflective mirror formed of spaced-apart plate-shaped empty space patterns formed within a substrate is disclosed. The plurality of plate-shaped empty space patterns are formed by drilling holes in the substrate and annealing the substrate to form the spaced-apart plate-shaped empty space patterns.

FIELD OF THE INVENTION

The present invention relates to semiconductor devices and methods of making such devices. More particularly, the invention relates to solid state materials and to a novel method of forming multi-layered dielectric mirrors including empty-spaced patterns formed in such solid materials.

BACKGROUND OF THE INVENTION

Monocrystalline solid state materials such as single-crystal semiconductors are the basis of the current microelectronics industry. Solid state materials are characterized by a variety of properties, for example, electrical properties such as electrical conductivity or charge mobility, optical properties such as refractive index or speed of photons, thermal properties such as thermal conductivity or thermal expansion, mechanical properties such as stress or strain curves, and chemical properties such as resistance to corrosion or reaction consistency, among others.

Over the past years, the semiconductor industry has constantly explored new ways of increasing the amount of active surface area on the integrated circuit chips, particularly on those employing monocrystalline semiconductor substrates. Accordingly, attempts to modify the electrical, optical, thermal and/or mechanical properties of such monocrystalline substrates have been made in an effort to minimize the dimensions of the IC devices, while maximizing the corresponding available active area. For example, new epitaxial growth processes such as the Epitaxial Lateral Overgrowth (ELO) have been used in an attempt to extend the amount of surface area available to active devices. However, these growth processes have limited results mainly because they consume part of the precious surface areas for seeding purposes, defeating therefore the primary purpose of increasing the available active area.

Another technology proposed by the semiconductor industry is the so-called Silicon-On-Insulator (SOI) process, wherein oxygen atoms are implanted at high dose and energy to form a silicon dioxide insulating layer between the upper surface of the original monocrystalline substrate and the bottom bulk portion of the same substrate. Although the SOI devices have many advantages, such as reduced parasitic capacitance due to the buried insulating layer, the process is relatively expensive because of the high costs of implanting the oxygen atoms and curing of the implant-induced defects.

Thin-film technology, including the formation of multi-layered dielectrics, is another highly developed technology in the semiconductor industry, which is widely used for the control of the reflection and/or transmission of light or radiant heat at optical surfaces. When monochromatic light falls on a thin transparent film dielectric having a thickness “d,” the light waves reflected from the front and the rear surfaces of the dielectric film interfere. For near-normal incidence, the conditions for a maximum or minimum intensity of the light reflected from such film dielectric depend on the index of refraction of the film dielectric as follows: 2nd=(k+½)λ maxima  (1) and 2nd=kλ minima  (2) wherein:

-   -   n=index of refraction of the dielectric;     -   λ=wavelength of a monochromatic light entering the dielectric;     -   d=thickness of the dielectric; and     -   k=0, 1, 2, . . . .

Equations (1) and (2) apply when the index of refraction “n” of the dielectric film is greater or less than the indices of the media on each side of the dielectric. Only in these cases, there will be a relative phase change of 180° for reflections at the two surfaces. A glass plate in air or an air film between two glass plates provide examples of cases to which both equations (1) and (2) apply.

Accordingly, there is a need for an improved method of increasing the available active surface area on integrated circuit chips fabricated on monocrystalline substrates which involve the transmission and/or reflection of light. There is also a need for a more advantageous method of forming dielectric mirrors in monocrystalline semiconducting substrates for low power dissipation, low light losses and high speed optoelectronic devices.

SUMMARY OF THE INVENTION

The present invention provides a method of forming multi-layered dielectric mirrors in light-transmissive substrates, such as, for example, monocrystalline silicon or quartz substrates. According to an exemplary embodiment of the invention, a plurality of buried plate-shaped empty spaces are formed in a light-transmissive substrate. The plurality of such buried plate-shaped regions have indices of refraction greater or less than the index of refraction of the light-transmissive substrate within which they are formed. Particular optical properties of the dielectric mirrors and/or bulk material within which they are formed can be easily tailored by the bulk material and the location, size and number of plate-shaped empty spaces formed therein.

These and other features and advantages of the invention will be more clearly apparent from the following detailed description which is provided in connection with accompanying drawings and which illustrates exemplary embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1(a)-(f) illustrate a portion of a silicon substrate undertaking a sequence of steps for single sphere-shaped empty space formation.

FIGS. 2(a)-(c) illustrate a portion of a silicon substrate undertaking a sequence of steps for single pipe-shaped empty space formation.

FIGS. 3(a)-(b) illustrate a portion of a silicon substrate undertaking a sequence of steps for plate-shaped empty space formation, performed in accordance with a method of forming a multi-layered mirror of the present invention.

FIG. 4 is a cross-sectional view of the representative silicon structure of FIG. 3(a), taken along line 4-4′, at an intermediate stage of processing and in accordance with a first embodiment of the present invention.

FIG. 5 is a three-dimensional view of the representative silicon structure according to the present invention at a stage of processing subsequent to that shown in FIG. 4.

FIG. 6 is a three-dimensional view of the representative silicon structure according to the present invention at a stage of processing subsequent to that shown in FIG. 5.

FIG. 7 is a three-dimensional view of the representative silicon structure according to the present invention at a stage of processing subsequent to that shown in FIG. 6.

FIG. 8 is a cross-sectional view of the representative multi-layer empty plate according to the present invention.

FIG. 9 is a schematic cross-sectional view of a laser assembly fabricated in accordance with the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

In the following detailed description, reference is made to various exemplary embodiments for carrying out the invention. These embodiments are described with sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be employed, and that structural, electrical and process changes may be made, and equivalents substituted, without departing from the invention. Accordingly, the following detailed description is exemplary and the scope of the present invention is defined by the appended claims.

The term “substrate” used in the following description includes any light-transmissive material having a uniform structure and a reasonably defined melting temperature. The term “substrate” is to be understood as including substrates formed of silicon, quartz, glass, gallium arsenide, indium gallium arsenide, silicon-on-insulator, doped and undoped semiconductors, epitaxial layers of silicon supported by a base semiconductor foundation, and other semiconductor and dielectric structures, as long as they retain a uniform and/or transparent structure and a defined melting temperature. Furthermore, when reference is made to a substrate in the following description, previous process steps may have been utilized to form regions or junctions in the base semiconductor structure or foundation.

The following discussion illustrates formation of a multi-layer dielectric mirror in a silicon substrate. The invention may be employed with other substrate materials noted, including quartz, and calculations are provided for both silicon and quartz substrates. However, it should be apparent to one skilled in the art that calculations may be used with any substrate having a uniform structural reasonably defined melting temperature.

Referring now to the drawings, where like elements are designated by like reference numerals, FIGS. 4-8 illustrate exemplary embodiments of a multi-layered dielectric mirror 100 comprising plate-shaped empty-spaced patterns formed in accordance with the present invention.

Before discussing the invention with specific reference to FIGS. 4-8, a background discussion of empty-spaced pattern formation in a substrate, such as silicon substrate 10 of FIG. 1, will be described with reference to FIGS. 1-3. Techniques for the formation of empty-spaced patterns of different geometries are described by Sato et al., in Substrate Engineering for the Formation of Empty Space in Silicon (ESS) Induced by Silicon Surface Migration, 1999 IEDM Digest, Paper 20.6.1, the disclosure of which is incorporated by reference herein.

Empty spaces which are formed in silicon substrates and have various shapes, such as plates, spheres or pipes, may be formed as a result of the self-organizing migration properties on the silicon surface. As such, when deeply-etched silicon substrates are annealed in a hydrogen ambient, for example, the silicon atoms on the surface migrate so that their surface energy is minimized. Based on these findings, Sato et al. have demonstrated that the geometry of empty spaces, such as spheres, plates and pipes, formed under the surface of a silicon substrate depends on the size, number and spacing of a plurality of cylindrical holes that are initially formed at a low temperature.

For example, FIGS. 1(a)-(f) illustrate how a single sphere-shaped empty space 13 is formed from a single cylindrical hole 12 formed within the silicon substrate 10. Subsequent to the formation of the cylindrical hole 12, the silicon substrate 10 is annealed at a temperature lower than the melting point of monocrystalline silicon (1400° C.), for example, at a temperature of about 1100° C. Sato et al. have demonstrated that, within about 60 seconds and under a reducing ambient of 10 Torr of hydrogen, the shape and surface morphology of the cylindrical hole 12 changes drastically to that of the sphere-shaped empty space 13 (FIG. 1(f)). Because of the significant surface and/or volume diffusion which occurs at high annealing temperatures, the cylindrical hole 12 is unstable beyond a critical length Lc and transforms, therefore, to a lower energy state consisting of one or more empty spheres formed along the original cylinder axis.

As analyzed by Nichols et al., in Surface- (Interface-) and Volume-Diffusion Contributions to Morphological Changes Driven by Capillarity, Trans. AIME 233 at 1840 (October 1965), the disclosure of which is incorporated by reference herein, the number N of empty spheres that form from a cylindrical hole depends both on the length L of the cylindrical hole and on the cylinder radius Rc. Accordingly, the number N of empty spheres formed from a cylindrical hole made in a silicon substrate can be estimated according to the following equation: 8.89Rc N≦L<8.89Rc(N+1)  (3) wherein:

-   -   N=number of empty spheres;     -   Rc=cylinder radius; and     -   L=length of cylindrical hole.

Thus, equation (3) predicts that, if L<8.89 Rc, the number of empty spheres will be N=0, which means that no empty spheres will form from a cylindrical hole.

When one or more empty spheres form with a radius Rs, then according to Nichols et al., the value of Rs is given by the following equation: Rs=1.88Rc  (4) wherein:

-   -   Rs=sphere radius; and     -   Rc=cylinder radius.

When two or more empty spheres form from a cylinder hole with a cylinder radius Rc, then the distance 1 between the centers of two adjacent empty-spaced spheres is calculated from the following formula: 1=8.89Rc  (5) wherein:

-   -   1=center-to-center distance between two adjacent spheres; and     -   Rc=cylinder radius.

Reference is now made to FIGS. 2(a)-(c), which exemplify the formation of a single pipe-shaped empty space 23 from a linear array of cylindrical holes 22. Similarly, FIGS. 3(a)-(b) illustrate the formation of a single plate-shaped empty space 33 from a two-dimensional array of cylindrical holes 32 formed within a silicon substrate such as the silicon substrate 10. The values of the pipe radius Rp (of the pipe-shaped empty space 23) and that of the plate thickness Tp (of the plate-shaped empty space 33) may be calculated in a manner similar to that described above with reference to the formation of the empty sphere 13 and the calculation of sphere radius Rs in equation (4). The distance Δ between the centers of any two adjacent cylindrical holes 22, 32, in a linear array, may be calculated from the following formula: 2Rc<Δ<3.76Rc  (6) wherein:

-   -   Rc=cylinder radius; and     -   Δ=center-to-center distance between two adjacent cylinder holes         in a linear array.

Equation (6) ensures that adjacent cylindrical holes 22, 32 do not touch each other allowing, therefore, the formation of a plurality of adjacent spheres that combine to form the resulting pipe-shaped empty space 23 and plate-shaped empty space 33.

The values of the pipe radius Rp and of the plate thickness Tp are given by the following two expressions: Rp=(8.86Rc ³/Δ)^(1/2)  (7) Tp=27.83Rc ³/Δ²  (8) wherein:

-   -   Rp=pipe radius;     -   Tp=plate thickness; and     -   Δ=center-to-center distance between two adjacent cylinder holes         in a linear array.

Reference is now made to FIG. 4 which, for simplicity, illustrates a cross-sectional view of structure of FIG. 3(a) on which a plurality of two-dimensional array of cylindrical holes 32 are drilled into silicon substrate 10 from an upper surface 11 of the substrate 10 to a depth D1.

The silicon substrate 10 is annealed at a temperature of about 1100° C. and under a reducing ambient of about 10 Torr of hydrogen, so that within about 60 seconds the two-dimensional array of cylindrical holes 32 transforms into the first plate-shaped empty space 33 (FIG. 5) by steps similar to those described above with reference to FIGS. 3(a)-(b). For a better understanding of the invention, the structure of FIG. 5 is illustrated in a three-dimensional view.

Radius R1 (FIG. 4) as well as distance Δ1 (FIG. 4) between the center of two adjacent cylindrical holes 32 of the two-dimensional array may be calculated in accordance to equation (6). Further, the length L1 (FIG. 4) of the two-dimensional array of cylindrical holes determines the length L1 (FIG. 5) of the first plate-shaped empty space 33, wherein the depth D1 (FIG. 4) to which the two-dimensional array of cylindrical holes is drilled determines the depth D1 (FIG. 5) at which the first plate-shaped empty space 33 is formed within the silicon substrate 10. In this case, the depth D1 and radius R1 of the cylindrical holes are chosen so that a single plate-shaped empty space, for example the first plate-shaped empty space 33, is formed at depth D1.

The thickness d (FIG. 5) of the first plate-shaped empty space 33 may be calculated in accordance with equation (8), where Tp=d₁. As known in the art, this first plate-shaped empty region may be left empty in some areas, so that the region above the plate becomes a silicon-over-nothing area.

Subsequent to the formation of the first plate-shaped empty space 33, a second plate-shaped empty space 35 (FIG. 7) may be formed above the first plate-shaped empty space 33 and below the silicon surface 11 by a technique similar to that described for the formation of the first plate-shaped empty space 33 (FIGS. 5-6). As such, a second two-dimensional array of cylindrical holes 34 (FIG. 6) are drilled into the silicon substrate 10 to a depth D2 to define the intended location, length and orientation of a second plate-shaped empty space 33 (FIG. 7). The silicon substrate 10 is then annealed at a temperature of about 1100° C. and under a reducing ambient of about 10 Torr of hydrogen, so that within about 60 seconds the second two-dimensional array of cylindrical holes 34 transforms into the second plate-shaped empty space 35 (FIG. 7) by steps similar to those described above with reference to FIGS. 3(a)-(b).

Radius R2 (FIG. 6) as well as distance A2 (FIG. 6) between the center of two adjacent cylindrical holes 34 of the second two-dimensional array may be calculated in accordance to equation (6). Further, the length L2 (FIG. 6) of the second two-dimensional array of cylindrical holes determines the length L2 (FIG. 7) of the second plate-shaped empty space 35, wherein the depth D2 (FIG. 6) to which the second two-dimensional array of cylindrical holes is drilled determines the depth D2 (FIG. 7) at which the second plate-shaped empty space 35 is formed within the silicon substrate 10. The thickness d (FIG. 7) of the second plate-shaped empty space 33 may be calculated in accordance with equation (8), where Tp=d₂.

Although FIG. 7 depicts only two plate-shaped empty spaces 33, 35 formed within the silicon substrate 10, it must be understood that any number “N” of such plate-shaped empty spaces may be formed by repeated application of the process described above and depicted in FIGS. 4-7. Such an “N” step process is required for the formation of a mirror with plate-shaped empty spaces having different thicknesses and/or being spaced non-uniformly. In the case where each plate-shaped empty space has an identical thickness “d” and the thickness of the material layers between any adjacent empty space is h₁ and the refractive index of each material layer is n₁ as shown in FIG. 8, it is only necessary to drill one, two-dimensional array of cylindrical holes and to undergo one high-temperature anneal step to simultaneously form the N plate-shaped empty spaces depicted in FIG. 8. The formation of a multi-layered dielectric mirror formed in this manner is described in detail below.

As illustrated in FIG. 8, the thickness of each of the N plate-shaped empty spaces is “d,” the refraction index of each of the plate-shaped empty spaces is n=1 (for air), the thickness of the material layers between any adjacent plate-shaped empty spaces is h₁ and the refraction index of each material layer is n₁. Applying these parameters to equation (1), the reflectivity R_(N) for the multi-layered dielectric mirror 100 is maximum at a free space wavelength λ when both equations (9) and (10) below are true: 2dn=2d=(m+½)λ  (9) wherein:

-   -   d=thickness of each plate-shaped empty space;     -   n=refraction index of each plate-shaped empty space;     -   λ=wavelength for which mirror reflectivity is maximum; and     -   m=0, 1, 2, 3, . . . and         2h ₁ n ₁=(k+½)λ  (10)         wherein:     -   h1=thickness of material layers between adjacent plate-shaped         empty spaces;     -   n₁=refraction index of each material layer;     -   λ=wavelength for which mirror reflectivity is maximum; and     -   k=0, 1, 2, 3 . . . .

The reflectivity R_(N) for the multi-layered dielectric mirror 100 of FIG. 8 comprising N plate-shaped empty spaces formed as described above is given by the following formula: R _(N)=(1−n ₁ ^(2N+1)/1+n ₁ ^(2N+1))²  (11) wherein:

-   -   R_(N)=maximum reflectivity of mirror;     -   n₁=refraction index of each material layer; and     -   N=number of plate-shaped empty spaces.

As such, equation (11) permits the calculation of R_(N) for various material monocrystalline layers. For example, illustrated below are the values of R_(N) for N=7 plate-shaped empty spaces formed in a quartz (SiO₂) substrate (SiO₂ refraction index is n₁=1.54) and in a silicon (Si) substrate (Si refraction index is n₁=3.44), such as the silicon substrate 10: R_(N) for SiO₂ R_(N) for Si N = 0 0.045 0.302 N = 1 0.165 0.838 N = 2 0.487 0.971 N = 3 0.741 0.9975 N = 4 0.881 0.9997 N = 5 0.942 ≅1 N = 6 0.977 ≅1 N = 7 0.991 ≅1

Further, when the reflectivity R_(N) for the multi-layered dielectric mirror 100 is maximum at a free space wavelength λ, the required radius Rc and separation Δ_(N) of initial cylinders may be calculated accordingly. Thus, if 1=h₁+d (as shown in FIG. 8), and applying equations (5), (9) and (10) it follows that: $\begin{matrix} {{Rc} = {{1/8.89} = {{\left( {h_{1} + d} \right)/8.89}\quad = {{\lambda/{4\left\lbrack {{\left( {{2k} + 1} \right)/{n1}} + \left( {{2m} + 1} \right)} \right\rbrack}}\left( {1/8.89} \right)}}}} & (12) \end{matrix}$

Next, when the plate thickness Tp equals d and applying the value of Rc (as calculated in equation 12) to equation (8), the center-to-center distance Δ_(N) between two adjacent cylindrical holes in a linear array may be calculated as follows: Δ_(N) ²=27.83Rc ³ /d=27.83Rc ³/(2m+1)λ/4  (13) wherein:

-   -   Δ_(N)=center-to-center distance between two adjacent cylindrical         holes;     -   Rc=cylinder radius;     -   λ=wavelength for which mirror reflectivity is maximum; and     -   m=0, 1, 2, 3, . . . ,     -   as long as the values of k and m from the equations (12)         and (13) satisfy the equation (14) below:         2Rc<Δ _(N)<3.76Rc  (14)         wherein:     -   Rc=radius of cylindrical hole; and     -   Δ_(N)=center-to-center distance between two adjacent cylindrical         holes.

Accordingly, applying the value of Δ_(N) from equation (13) to equation (14), it follows that: 2²<3.13{[(1/n1)(2k+1)(2m+1)]+1}<3.76²  (15)

-   -   which must be satisfied by both k and m so that maximum         reflectivity can be attained for a mirror fabricated by a method         of the present invention.

For illustration, in a case where the material layers are formed of SiO₂ (quartz) for which the refraction index is n₁=1.54, and where the wavelength λ=0.2 micron and the number of plate-shaped empty spaces are N=7, then equation (15) is satisfied because real solutions for both k and m exist since: 4<3.13[0.649(2k+1)(2m+1)+1]<14.76  (16)

Further, when quartz is used as the substrate and assuming that k=m=0; n₁=1.54; and the wavelength λ=0.2 microns, the values of the cylinder radius “Rc,” the thickness “d” of the plate-shaped empty space, the thickness “h₁” of the quartz layers between adjacent plate-shaped empty spaces, as well as the center-to-center distance Δ_(N) between two adjacent cylindrical holes may be calculated according to equations (5), (9), (10) and (13), respectively, to obtain the following values:

-   -   Rc=0.00928 microns;     -   h₁=0.03256 microns;     -   d=0.05 microns; and     -   Δ_(N)=0.021 microns.

Also, the length L of a cylindrical hole could be also calculated from the above parameters as applied to equation (3) as follows: 0.5775 microns≦L<0.6560 microns  (17)

By using larger integer values for k and/or m, the values of “Rc,” “d,” “h₁” and “Δ_(N)” may be increased accordingly. If the value of L is chosen as the lower limit (for example, as the lower limit 0.5775 from equation (17) corresponding to N=7 for multi-layered quartz), the top surface above the plate-shaped empty spaces will be at the same level as the top surface 11 of the substrate 10. If, however, the value of L is chosen as the upper limit (for example, as the upper limit 0.6560 from equation (17) corresponding to N=7 and quartz layers) or at least greater than the lower limit, then the top surface above the plate-shaped empty spaces will be lower than the to surface 11 of substrate 10, as illustrated in FIG. 8.

When quartz is used as the monocrystalline substrate material, the annealing temperature for the formation of the plate-shaped empty spaces 33, 35, for example, could be higher than the annealing temperature of about 1100° C. used for a silicon substrate. Since the melting temperature of quartz is of about 1610° C. and, thus, higher than the melting temperature of silicon which is of about 1400° C., an annealing temperature of about 1100° C. and even higher could be used for the formation of a quartz mirror by the methods described above. Further, to avoid the loss of oxygen from the quartz material, an oxidizing rather than reducing ambient atmosphere could be used for the formation of the plate-shaped empty spaces. In any event, since the multi-layered dielectric mirror 100 utilizes only one material, such as silicon or quartz, among others, low internal loss is easily achieved.

Although the present invention has been described above with reference to the formation of reflective mirrors in silicon and quartz substrates, it must be understood that any substrate material having a uniform composition in the area of interest and a reasonably defined melting point may be used also. The annealing temperature for the formation of the plate-shaped empty spaces in such substrate material must be calculated and experimentally determined on a case-by-case analysis, as the annealing temperatures for forming empty spaces by surface transformation in substrates other than silicon and quartz have not been calculated yet by those skilled in the art. In any event, the annealing temperature must be lower than the melting point of such substrate material. The annealing temperature also depends greatly upon the self-organizing migrating properties of the substrate material to achieve minimal surface energy, as well as upon the reaction time and the extend of damage inflicted to the surfaces where cylindrical holes are drilled.

Although the present invention has been specifically described above with reference to the multi-layered dielectric mirror 100 formed of N=7 plate-shaped empty spaces, it must be understood that the present invention contemplates the formation of a reflective mirror with any number “N” of such plate-shaped empty spaces. As such, the invention contemplates, for example, the formation of a reflective mirror with only one plate-shaped empty space. In that case, however, the mirror reflectivity R_(N) is much lower than that for a mirror having multiple plate-shaped empty spaces. For example, as calculated above with reference to equation (11), the maximum reflectivity of a mirror for silicon is of about 0.838, meaning that the single plate-shaped empty space mirror has a reflectivity of about 83% only. As known in the art, such a mirror could be useful as an output mirror of a laser which requires only about 80% reflectivity.

The formation of the multi-layered dielectric mirror 100 was described above with reference to N=7 plate-shaped empty spaces having same thicknesses and been spaced apart uniformly. It must be understood, however, that the present invention contemplates the formation of a reflective mirror with plate-shaped empty spaces having different thicknesses and/or being spaced apart non-uniformly. In such cases, the plate-shaped empty spaces will have different reflectivities and different phase-shifts, depending on the respective thickness and refractive index corresponding to each plate-shaped empty space. The general formula for calculating the reflectivity from periodically stratified media where there is no requirement on thicknesses and/or indices is very complex but may be found in Section 1.6.5 entitled “Periodically Stratified Media” in M. Born and E. Wolf, Principles of Optics at pp. 65-69, (Pergamon Press 1959), the disclosure of which is incorporated by reference herein.

The multi-layered dielectric mirror 100 formed by the method of the present invention described above could be used, for example, as a patterned reflective mask which can withstand high incident power levels, or as a high-reflectivity mirror below the junction of a vertical cavity laser. The multi-layered dielectric mirror 100 of the present invention may be also used as one or more embedded mirrors 33 in the end faces of an optically pumped solid state ion laser assembly 200, comprising a body 210 for producing laser light, which is illustrated in FIG. 9.

The above description and drawings are only to be considered illustrative of exemplary embodiments which achieve the features and advantages of the present invention. Modification and substitutions to specific process conditions and structures can be made without departing from the spirit and scope of the present invention. Accordingly, the invention is not to be considered as being limited by the foregoing description and drawings, but is only limited by the scope of the appended claims. 

1-22. (canceled)
 23. A method of modifying the transmission of an electromagnetic wave, said method comprising the steps of: transmitting said electromagnetic wave through a monocrystalline substrate, said monocrystalline substrate comprising at least one plate-shaped empty spaced pattern within, and surrounded by, said monocrystalline substrate, and below a surface of said monocrystalline substrate, said at least one plate-shaped empty spaced pattern being positioned along a transmission axis of said electromagnetic wave; and phase-shifting said electromagnetic wave as it passes through said monocrystalline substrate.
 24. The method of claim 23, wherein said electromagnetic wave is phase-shifted about 180 degrees.
 25. The method of claim 23 further comprising the act of forming at least one hole within said monocrystalline substrate and annealing said monocrystalline substrate to form said at least one plate-shaped empty spaced pattern beneath said surface of said monocrystalline substrate.
 26. The method of claim 25, wherein said act of annealing is performed under a reducing atmosphere.
 27. The method of claim 26, wherein said reducing atmosphere is a hydrogen atmosphere at a temperature lower than the melting temperature of said monocrystalline substrate.
 28. The method of claim 23 further comprising the act of forming at least two plate-shaped empty spaced patterns positioned along said transmission axis of said electromagnetic wave.
 29. The method of claim 28, wherein said at least two plate-shaped empty spaced patterns are formed sequentially.
 30. The method of claim 28, wherein said at least two plate-shaped empty spaced patterns are formed simultaneously.
 31. The method of claim 30, wherein one of said plate-shaped empty spaced patterns is located below said other plate-shaped empty spaced pattern relative to said surface of said monocrystalline substrate.
 32. The method of claim 30, wherein said plate-shaped empty spaced patterns have same thicknesses.
 33. The method of claim 30, wherein said plate-shaped empty spaced patterns have different thicknesses.
 34. The method of claim 23, wherein said monocrystalline substrate is a germanium substrate.
 35. The method of claim 23, wherein said monocrystalline substrate is a silicon substrate.
 36. The method of claim 23, wherein said monocrystalline substrate is a silicon-on-insulator substrate.
 37. The method of claim 23, wherein said monocrystalline substrate is a silicon-on-nothing substrate.
 38. The method of claim 23, wherein said monocrystalline substrate is a gallium arsenide substrate. 39-81. (canceled) 